Thermoplastic resin composition and use thereof

Abstract

The present invention aims to obtain a thermoplastic resin composition which is suitable for obtaining a molded body which does not cause an increase in hydrophilicity, has a hard feel, and has a texture closer to that of pottery. The thermoplastic resin composition of the present invention is characterized by comprising 10 to 50 parts by mass of a thermoplastic resin (A), 50 to 90 parts by mass of a metal oxide (B) [wherein the total amount of (A) + (B) is 100 parts by mass], and, relative to the total amount of (A) + (B): 100 parts by mass, an unmodified polyolefin-based wax (C) in the range of 0.1 to 20 parts by mass.

Description

Technical Field

[0001] This invention relates to thermoplastic resin compositions containing metal oxides and their uses. Background Technology

[0002] Thermoplastic resins such as polyolefins and ABS are molded using various methods and used for a wide range of applications. On the other hand, polyolefins such as polypropylene have poorer mechanical properties such as heat resistance, rigidity, and tensile strength compared to engineering plastics such as polyamide and polycarbonate. Therefore, depending on the application, inorganic fillers such as talc and heat-resistant fibers such as glass fiber and carbon fiber are added as reinforcing materials.

[0003] For example, Patent Document 1 proposes a polyolefin composition containing 20 to 80 parts by weight of an inorganic filler formed from an inorganic compound.

[0004] On the other hand, it has been found that the compatibility with polyolefins is poor when a large amount of inorganic compounds such as metal oxides are incorporated. In order to improve the compatibility, for example, in Patent Document 2, a scheme is proposed to incorporate 0.1 to 20 parts by mass of modified polyolefin wax into a composition containing 10 to 50 parts by mass of thermoplastic resin and 50 to 90 parts by mass of metal oxide.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 52-15542

[0008] Patent Document 2: International Publication No. 2017 / 209215 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, it has been found that, in the case of thermoplastic resin compositions obtained by combining modified polyolefin waxes, the surface hydroxyl density of the resulting molded body tends to increase, resulting in higher hydrophilicity and a wet texture. In addition, under certain conditions (such as acid solutions), inorganic compounds may dissolve, causing a decrease in texture.

[0011] The object of the present invention is to obtain a thermoplastic resin composition suitable for obtaining molded articles that do not lead to an increase in hydrophilicity (low water absorption), have a hard texture, and have a texture closer to that of pottery.

[0012] Methods for solving problems

[0013] The present invention relates to, for example, the following [1] to

[20] .

[0014] In this specification, the term "polymer" includes both homopolymers and copolymers unless otherwise specified.

[0015] [1] A thermoplastic resin composition comprising 10 to 50 parts by weight of a thermoplastic resin (A), 50 to 90 parts by weight of a metal oxide (B) [wherein the total amount of (A) + (B) is set to 100 parts by weight], and unmodified polyolefin wax (C) in the range of 0.1 to 20 parts by weight relative to the total amount of (A) + (B): 100 parts by weight.

[0016] [2] The thermoplastic resin composition as described in [1], wherein the aforementioned thermoplastic resin (A) is selected from one or more of the group consisting of ethylene polymers, propylene polymers, 1-butene polymers, 4-methyl-1-pentene polymers, and ABS resins.

[0017] [3] The thermoplastic resin composition as described in [1] or [2], wherein the aforementioned metal oxide (B) comprises magnesium oxide.

[0018] [4] The thermoplastic resin composition as described in any one of [1] to [3], wherein the average particle size of the aforementioned metal oxide (B) is in the range of 0.1 to 110 μm.

[0019] [5] The thermoplastic resin composition as described in any one of [1] to [4], wherein the thermal conductivity of the aforementioned metal oxide (B) is in the range of 10 to 300 W / mK.

[0020] [6] The thermoplastic resin composition as described in any one of [1] to [5], wherein the thermal conductivity of the aforementioned thermoplastic resin composition is in the range of 0.5 to 5 W / mK.

[0021] [7] The thermoplastic resin composition as described in any one of [1] to [6], wherein the specific gravity of the aforementioned thermoplastic resin composition is in the range of 1.0 to 5.0.

[0022] [8] The thermoplastic resin composition as described in any one of [1] to [7], comprising 10 to 30 parts by weight of the aforementioned thermoplastic resin (A) and 70 to 90 parts by weight of the aforementioned metal oxide (B) [wherein the total amount of (A) + (B) is set to 100 parts by weight].

[0023] [9] The thermoplastic resin composition according to any one of [1] to [8], wherein, in an antibacterial test using Escherichia coli in accordance with JIS Z 2801:2012 (membrane sealing method), the antibacterial activity value is 2.0 or higher after 24 hours without water resistance and light resistance pretreatment.

[0024]

[10] The thermoplastic resin composition according to any one of [1] to [9], wherein, in an antibacterial test using Staphylococcus aureus in accordance with JIS Z 2801:2012 (membrane sealing method), the antibacterial activity value is 2.0 or higher after 24 hours without water resistance and light resistance pretreatment.

[0025]

[11] The thermoplastic resin composition as described in any one of [1] to

[10] , wherein the antiviral activity value is 2.0 or higher in an antiviral test performed in accordance with ISO 21702:2019 using feline calicivirus.

[0026]

[12] The thermoplastic resin composition as described in any one of [1] to

[11] includes a fibrous filler (D) in the range of 0.1 to 20 parts by mass relative to a total of 100 parts by mass of the aforementioned thermoplastic resin (A) and the aforementioned metal oxide (B).

[0027]

[13] A molded body comprising any one of the thermoplastic resin compositions described in [1] to

[12] .

[0028]

[14] A door handle, a door knob, a handrail or switch, comprising any one of the thermoplastic resin compositions described in [1] to

[12] .

[0029]

[15] A housing comprising the thermoplastic resin composition described in any one of [1] to

[12] .

[0030]

[16] Apparel accessories comprising any one of the thermoplastic resin compositions described in [1] to

[12] .

[0031]

[17] A container comprising the thermoplastic resin composition described in any one of [1] to

[12] .

[0032]

[18] Stationery comprising any one of the thermoplastic resin compositions described in [1] to

[12] .

[0033]

[19] Tableware or wine vessels comprising any one of the thermoplastic resin compositions described in [1] to

[12] .

[0034]

[20] A mouse or keyboard comprising any one of the thermoplastic resin compositions described in [1] to

[12] .

[0035] Invention Effects

[0036] The thermoplastic resin composition of the present invention has extremely low water absorption and thermal conductivity comparable to that of ceramics, thus making it suitable for obtaining molded articles with a cool touch, a hard texture, and a feel closer to that of ceramics. Furthermore, the presence of the incorporated metal oxide imparts antibacterial properties to the product of the present invention, making it suitable for obtaining molded articles intended for direct touch to perceive their texture. Detailed Implementation

[0037] The present invention will now be described in detail.

[0038] <Thermoplastic Resin (A)>

[0039] Thermoplastic resin (A), one of the components included in the thermoplastic resin composition of the present invention, can be, for example, an olefin polymer, an ABS resin, a styrene resin, a polyester, etc.

[0040] Olefin polymers are homopolymers of α-olefins (including ethylene), such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene; copolymers of the aforementioned α-olefins with other α-olefins; and copolymers of the aforementioned α-olefins with monomers other than α-olefins, and polymers with α-olefins as the main component.

[0041] Specifically, the following polymers can be cited as examples of the thermoplastic resin (A) involved in this invention.

[0042] <Ethylene polymers (A1)>

[0043] The ethylene-based polymers (A1) involved in this invention are homopolymers of ethylene, copolymers of ethylene and α-olefins having 3 to 20 carbon atoms, and are generally known as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ethylene-α-olefin copolymers, polymers whose main components are structural units derived from ethylene. Specific examples of α-olefins with 3 to 20 carbon atoms copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, and 3,5,5-trimethyl-1-hexene. Preferably, the α-olefin has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. The molar ratio of ethylene to α-olefin (ethylene / α-olefin) is preferably 99 / 1 to 60 / 40, more preferably 95 / 5 to 70 / 30, and even more preferably 90 / 10 to 60 / 25.

[0044] Preferred examples of ethylene-α-olefin copolymers include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-1-octene copolymers, ethylene-propylene-1-butene copolymers, and ethylene-propylene-1-octene copolymers. Among these, ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-1-pentene copolymers, and ethylene-1-octene copolymers are preferred, and ethylene-1-butene copolymers are more preferred.

[0045] The density of the ethylene polymer (A1) (determined according to JIS K7112) is preferably 850–980 kg / m³. 3 More preferably, it is 855–978 kg / m³. 3 A further preferred value is 860–976 kg / m³. 3 The preferred strength is 862–973 kg / m³. 3 .

[0046] When the thermoplastic resin composition of the present invention contains an ethylene-based polymer (A1), the molded articles obtained from the thermoplastic resin composition tend to have higher thermal conductivity and better temperature sensitivity compared to those containing an propylene-based polymer (A2), and also produce a higher sound when struck. Such molded articles can be suitably used in a variety of applications without limitation, for example, they can be suitably used as a base raw material for surface modification in metal vapor deposition.

[0047] <Propylene polymers (A2)>

[0048] The propylene-based polymers (A2) involved in this invention are polymers whose main components are structural units derived from propylene, such as homopolymers of propylene (propylene homopolymer: homopolymer PP), copolymers of propylene with ethylene and / or α-olefins having 4 to 20 carbon atoms (random copolymer: random copolymer: random PP), and compositions of homopolymers of propylene with ethylene-propylene copolymers (block copolymer: block copolymer: block PP). Specific examples of α-olefins in propylene-α-olefin copolymers include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-hexene, and 3,5,5-trimethyl-1-hexene. The preferred components are ethylene and α-olefins having 4 to 10 carbon atoms, more preferably ethylene and α-olefins having 4 to 8 carbon atoms, and particularly preferably ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. The molar ratio of propylene to α-olefins (propylene / α-olefin) is preferably 99 / 1 to 60 / 40, more preferably 95 / 5 to 70 / 30, and even more preferably 90 / 10 to 70 / 30.

[0049] Preferred examples of propylene-α-olefin copolymers (random PP) include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, propylene-1-octene copolymers, and propylene-ethylene-1-butene copolymers. Among these, propylene-ethylene copolymers and propylene-1-butene copolymers are preferred, and propylene-ethylene copolymers are particularly preferred.

[0050] In the case of a propylene homopolymer, the preferred melting point is 155–170°C, and more preferably 158–165°C.

[0051] In the case of a propylene-ethylene random copolymer, the ethylene content of the propylene-ethylene random copolymer is preferably 1.9 to 5.4% by mass, more preferably 2.0 to 4.8% by mass. In addition, the crystal melting point of the propylene-ethylene random copolymer, as determined by differential scanning calorimetry (DSC) according to JIS K7121, is generally preferably 130 to 150°C, more preferably 130 to 145°C, and particularly preferably 135 to 145°C.

[0052] The density of the propylene polymer (A2) (determined according to JIS K7112) is preferably 850–910 kg / m³. 3 More preferably, it is 875–909 kg / m³.3 More preferably, it is 890–908 kg / m³. 3 .

[0053] The propylene polymer (A2) of the present invention can be a propylene polymer containing a fibrous filler (D) such as glass fiber, which will be described later. In this case, the density of the propylene polymer containing the fibrous filler (D) (measured according to JIS K7112) is preferably 910 to 1220 kg / m³. 3 More preferably, it is 940–1200 kg / m³. 3 A further preferred value is 970–1160 kg / m³. 3 The preferred value is 1000-1120 kg / m³. 3 .

[0054] Propylene-ethylene block copolymers and propylene-ethylene random copolymers can be used alone or in combination of two or more copolymers. For example, two or more copolymers can be mixed to adjust the MFR.

[0055] When the thermoplastic resin composition of the present invention contains an propylene polymer (A2), the molded articles obtained from the thermoplastic resin composition can be used in a variety of applications without limitation. Since it has a thermal conductivity similar to that of pottery and a specific gravity similar to that of pottery, and on the other hand, it will not break like pottery due to impacts such as falling, it has excellent safety. Therefore, it can be used in applications such as tableware such as cups, containers, door handles and other applications that are touched by hand.

[0056] <1-Butene polymers (A3)>

[0057] The 1-butene-based polymers (A3) involved in this invention are homopolymers of 1-butene (polybutene) and copolymers of 1-butene with ethylene, propylene and α-olefins having 5 to 20 carbon atoms (1-butene-α-olefin copolymers), etc., which are polymers with structural units derived from 1-butene as the main components.

[0058] <4-Methyl-1-pentene polymers (A4)>

[0059] The 4-methyl-1-pentene polymer (A4) involved in this invention is a homopolymer of 4-methyl-1-pentene and a copolymer of 4-methyl-1-pentene with α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) (4-methyl-1-pentene·α-olefin copolymer), etc., which are polymers with structural units derived from 4-methyl-1-pentene as the main component.

[0060] Specific examples of α-olefins in 4-methyl-1-pentene·α-olefin copolymers include linear α-olefins with 2 to 20 carbon atoms (preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms) such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, as well as branched α-olefins with 5 to 20 carbon atoms (preferably 5 to 15 carbon atoms) such as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene. Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferred, with ethylene and propylene being particularly preferred. α-olefins can be derived from one or more of these compounds.

[0061] The molar ratio of 4-methyl-1-pentene to α-olefin (4-methyl-1-pentene / α-olefin) is preferably 55 / 45 to 90 / 10, more preferably 60 / 40 to 86 / 14, and even more preferably 68 / 32 to 85 / 15.

[0062] In one embodiment, for the 4-methyl-1-pentene polymer (A4), the temperature at which the loss tangent (tanδ) peaks, obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) within a temperature range of -40 to 150°C, is 0°C to 60°C, preferably 10°C to 50°C, more preferably 20°C to 45°C, and particularly preferably 25°C to 44°C.

[0063] The peak value of the tanδ of the 4-methyl-1-pentene polymer (A4) is 0.6 or more and 5.0 or less. The peak value of this tanδ is preferably 0.7 or more and 4.5 or less, more preferably 0.8 or more and 3.5 or less.

[0064] For tanδ, the storage elastic modulus (G') and loss elastic modulus (G”) obtained during the dynamic viscoelasticity measurement can be used as the ratio of storage elastic modulus (G') to loss elastic modulus (G”) (G” / G': loss tangent) to calculate it.

[0065] In this invention, the temperature at which tanδ reaches its peak value (maximum value) within the range of -40 to 150°C is defined as the temperature at which tanδ reaches its peak value (hereinafter referred to as the "tanδ peak temperature"), and the value of tanδ at this temperature is defined as the peak value of tanδ (hereinafter referred to as the "tanδ peak value"). It should be noted that the peak is considered to originate from the glass transition temperature of the 4-methyl-1-pentene polymer (A4).

[0066] In another embodiment, for the 4-methyl-1-pentene polymer (A4), the tanδ peak temperature obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) within a temperature range of -40 to 150°C is preferably 15°C or higher and 45°C or lower. Here, regarding the lower limit of the aforementioned tanδ peak temperature, it is more preferably 20°C or higher, and even more preferably 25°C or higher. Furthermore, in the exemplary embodiment of the present invention, the aforementioned tanδ peak temperature is 40°C or lower, but it may exceed 40°C as long as the purpose of this application is achieved. In a typical embodiment of the present invention, the aforementioned tanδ peak temperature is more preferably 20°C or higher and 45°C or lower, and even more preferably 25°C or higher and 43°C or lower. By setting the tanδ peak temperature to the above-mentioned temperature range, the value of tanδ at room temperature can be further increased.

[0067] For the 4-methyl-1-pentene polymer (A4), the tanδ peak value obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) within a temperature range of -40 to 150°C is preferably 0.6 to 5.0, more preferably 1.0 to 4.8, even more preferably 1.3 to 4.5, and particularly preferably 1.8 to 4.0. By setting the tanδ peak value within the above range, vibration absorption, material hardness, and conformability can be varied according to the speed of stretching and deformation.

[0068] The melting point (Tm) of the 4-methyl-1-pentene polymer (A4), as determined by differential scanning calorimetry (DSC), is preferably below 160°C or not observable, more preferably below 140°C or not observable, and even more preferably not observable. By satisfying this requirement, the compatibility with inorganic materials in the resin composition of the present invention is improved, thereby enhancing vibration absorption and stress mitigation.

[0069] The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A4) measured in decahydronaphthalene at 135°C is preferably 0.1 dL / g or more and 5.0 dL / g or less, more preferably 0.5 dL / g or more and 4.0 dL / g or less, and even more preferably 0.5 dL / g or more and 3.5 dL / g or less. The 4-methyl-1-pentene polymer (A4) with an intrinsic viscosity [η] within the above range facilitates the manufacture of the molded article.

[0070] The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A4) can be adjusted to the above range by adding hydrogen to control the molecular weight and polymerization activity in the polymerization-based manufacturing process.

[0071] For the aforementioned intrinsic viscosity [η], the viscosity increase rate ηsp (i.e. ηsp / c) of each polymer, calculated per unit concentration c, when different amounts of thermoplastic resin composition are dissolved in decahydronaphthalene at 135°C can be obtained as the reducing viscosity ηred. ηred is then extrapolated to the condition that the unit concentration c of the polymer is zero.

[0072] The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) of the 4-methyl-1-pentene polymer (A4), as determined by gel permeation chromatography (GPC) (molecular weight distribution: Mw / Mn), is preferably 1.0 to 3.5, more preferably 1.2 to 3.0, and even more preferably 1.5 to 2.8. 4-methyl-1-pentene polymers (A4) with the above-mentioned Mw / Mn range are less prone to the reduction in moldability caused by low molecular weight, low cubicity polymers, and are easier to mold.

[0073] Furthermore, the weight-average molecular weight (Mw) of the 4-methyl-1-pentene polymer (A4), as determined by gel permeation chromatography (GPC), is preferably 500 to 10,000,000 when converted to polystyrene, more preferably 1,000 to 5,000,000, and even more preferably 1,000 to 2,500,000.

[0074] The Mw / Mn and Mw of the 4-methyl-1-pentene polymer (A4) can be adjusted to the above range, for example, by using a metallocene catalyst.

[0075] For the aforementioned Mw and Mw / Mn, for example, a Waters ALC / GPC 150-C plus (differential refractometer detector integrated type) can be used as a liquid chromatograph, with two Tosoh GMH6-HT columns and two GMH6-HTL columns connected in series, using o-dichlorobenzene as the mobile phase medium, and analyzing the chromatogram obtained under the conditions of a flow rate of 1.0 ml / min and 140 °C using a standard curve with a standard polystyrene sample to determine the Mw / Mn ratio.

[0076] The density of the 4-methyl-1-pentene polymer (A4) (determined according to JIS K7112) is preferably 870–830 kg / m³. 3 More preferably, it is 865–830 kg / m³. 3 A further preferred value is 855–830 kg / m³. 3 It should be noted that details regarding the measurement conditions, etc., are as described in the Examples section below.

[0077] The density can be suitably changed by the proportion of comonomers in the 4-methyl-1-pentene polymer (A4), and polymers (A4) with densities within the above range are advantageous from the perspective of manufacturing molded articles.

[0078] When the thermoplastic resin composition of the present invention contains a 4-methyl-1-pentene polymer (A4), the molded articles obtained from the thermoplastic resin composition can be suitably used in a variety of applications without limitation. Compared with the case containing a propylene polymer (A2), such molded articles have excellent softness, impart a characteristic of easy heat transfer, and thus have the properties of being easy to bend upon touch and easily maintaining their shape at room temperature.

[0079] <ABS resin (A5)>

[0080] The ABS resin (A5) involved in this invention includes not only acrylonitrile-butadiene-styrene copolymers, but also graft copolymers obtained by grafting monomers containing aromatic vinyl groups and vinyl cyanide groups onto a rubber component made from butadiene-containing monomers, as well as copolymers made from other monomers capable of copolymerizing with aromatic vinyl groups and vinyl cyanide groups. Here, the rubber component is a component manufactured using conventionally known solution polymerization, bulk polymerization, emulsion polymerization, etc. Furthermore, the aforementioned graft polymers formed with this rubber, or copolymers formed with this rubber, can be substances manufactured using any of the conventionally known solution polymerization, bulk polymerization, emulsion polymerization, etc., and are readily available on the market.

[0081] Specific examples of ABS resin (A5) include commercially available products such as KRALASTIC manufactured by NIPPON A&L INC., TECHNO ABS and UMG ABS manufactured by Techno-UMG Co., Ltd., TOYOLAC manufactured by Toray Industries, Inc., and Denka ABS manufactured by Denka Co., Ltd.

[0082] The density of ABS resin (A5) (determined according to ISO 1183) is preferably 1000–1070 kg / m³. 3 More preferably, it is 1001–1060 kg / m³. 3 More preferably, it is 1002–1050 kg / m³. 3 .

[0083] ABS resin (A5) can be used alone or in combination with two or more copolymers. For example, two or more copolymers can be mixed to adjust the MFR.

[0084] When the thermoplastic resin composition of the present invention contains ABS resin (A5), the molded articles obtained from the thermoplastic resin composition can be used in a variety of applications without limitation. Since it tends to have excellent impact resistance and high surface hardness compared with the case containing acrylic polymer (A2), it can be suitable for applications such as trays where object friction is envisioned, countertops, tables, bathroom counters, door handles where strength is required, etc.

[0085] <Other thermoplastic resins (A6)>

[0086] Examples of thermoplastic resins (A6) other than those listed in (A1) to (A5) include styrene-based resins such as polystyrene, polyesters such as PET, polyamides, and acrylic resins. These other thermoplastic resins (A6) can be manufactured by known methods, or commercially available products can be used. Other thermoplastic resins (A6) can be used alone or in combination of two or more.

[0087] Among these thermoplastic resins (A), olefin polymers (A1) to (A4) and ABS resin (A5) are preferred, and ethylene polymers (A1), propylene polymers (A2), 4-methyl-1-pentene polymers (A4), and ABS resin (A5) are more preferred. Two or more thermoplastic resins (A) may also be used together.

[0088] The medium-lowering flow rate (MFR) of the thermoplastic resin (A) (ASTM D1238, 230°C, 2.16 kg load) is preferably 7 to 300 g / 10 minutes. Here, considering the lower limit of the MFR, it is preferably 11 g / 10 minutes or more, more preferably 13 g / 10 minutes or more, further preferably 15 g / 10 minutes or more, and particularly preferably 18 g / 10 minutes or more. Furthermore, considering the upper limit of the MFR, it is preferably 200 g / 10 minutes or less, more preferably 150 g / 10 minutes or less, and further preferably 100 g / 10 minutes or less.

[0089] Thermoplastic resins (A) within the above range of MFR exhibit good moldability, such as injection molding properties, and the resulting molded articles also have good mechanical properties.

[0090] When the thermoplastic resin (A) is a 4-methyl-1-pentene polymer (A4), the upper limit of the MFR (ASTM D1238, 230°C, 2.16 kg load) is preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, further preferably 15 g / 10 min or less, and particularly preferably 13 g / 10 min or less.

[0091] When the thermoplastic resin (A) is an ethylene-based polymer (A1), the mean filtration rate (MFR) (ASTM D1238, 190°C, 2.16 kg load) is preferably 6 to 100 g / 10 minutes. Here, considering the lower limit of the MFR, it is preferably 8 g / 10 minutes or more, more preferably 10 g / 10 minutes or more, and even more preferably 11 g / 10 minutes or more. Furthermore, considering the upper limit of the MFR, it is preferably 80 g / 10 minutes or less, more preferably 60 g / 10 minutes or less, and even more preferably 50 g / 10 minutes or less.

[0092] When the thermoplastic resin (A) is ABS resin (A5), the MVR (ASTM D1133, 220℃, 10kg load) is preferably 10-100cm. 3 / 10 minutes. Here, from the lower limit side of MVR, 18cm is preferred. 3 / 10 minutes or more, preferably 30cm 3 / 10 minutes or more, further preferably 40cm 3 / 10 minutes or more. Additionally, considering the upper limit of the MVR, 95cm is preferred. 3 For 10 minutes or less, 90cm is preferred. 3 / less than 10 minutes, further preferably 85cm 3 / Less than 10 minutes.

[0093] <Metal Oxides (B)>

[0094] The metal oxide (B), which is one of the components included in the thermoplastic resin composition of the present invention, is not particularly limited in type as long as it is a metal oxide, but it is acceptable to use a metal oxide that has a higher thermal conductivity than the thermoplastic resin (A). For example, magnesium oxide (45-60 W / mK), aluminum oxide (17-36.0 W / mK), zinc oxide (25-54 W / mK), titanium oxide (8.4 W / mK), and other metal oxides can be used. Two or more metal oxides may also be used together. It should be noted that the value in parentheses after the substance name indicates the thermal conductivity at 300 K.

[0095] The metal oxide (B) involved in this invention is preferably a metal oxide with a thermal conductivity in the range of 10 to 300 W / mK. The lower limit of thermal conductivity is more preferably 15 W / mK, further preferably 20 W / mK, particularly preferably 30 W / mK, and most preferably 40 W / mK.

[0096] Furthermore, the upper limit of thermal conductivity is more preferably 250 W / mK, further preferably 200 W / mK, and particularly preferably 100 W / mK.

[0097] The thermoplastic resin composition obtained by mixing a metal oxide (B) with the thermoplastic resin (A) within the above-mentioned range has a suitable thermal conductivity. Therefore, it is possible to obtain molded articles such as containers that feel cool to the touch and warm when filled with hot objects.

[0098] In addition, unlike the case of using titanium dioxide as a photocatalyst, for metal oxides (B), magnesium oxide and zinc oxide are preferred in applications where light irradiation is not required and antibacterial and / or antiviral properties are required. Furthermore, magnesium oxide is more preferred from the perspective of its white color, ease of coloring, and low cost.

[0099] The metal oxide (B) involved in this invention can be in the shape of spheres, cubic shapes, plates, columns, hexagonal plates, etc., with spherical metal oxides being preferred. Alternatively, pulverized metal oxides (B) can also be used.

[0100] The metal oxide (B) involved in this invention preferably has an average particle size in the range of 0.1 to 110 μm. The lower limit of the average particle size is more preferably 0.2 μm, further preferably 0.5 μm, and particularly preferably 1 μm.

[0101] Furthermore, the upper limit of the average particle size is more preferably 105 μm, further preferably 90 μm, and particularly preferably 85 μm.

[0102] If the average particle size is too small, there are concerns that it is easy to agglomerate, the workability is reduced, and it is difficult to mix it uniformly with the thermoplastic resin (A). On the other hand, if the average particle size is too large, there are concerns that the thermal conductivity of the obtained thermoplastic resin composition becomes too low, and there are also concerns that the mechanical properties of the obtained molded article are reduced.

[0103] In applications requiring higher thermal conductivity, it is preferable to use, for example, metal oxides (b1) with an average particle size of 0.1 μm or more and less than 10 μm and metal oxides (b2) with an average particle size of 10 μm or more and less than 110 μm. In this case, the mixing ratio (mass ratio) is preferably (b1) / (b2) = 1 / 99 to 49 / 51, more preferably 5 / 95 to 45 / 55, and even more preferably 10 / 90 to 40 / 60.

[0104] By combining metal oxides (b1) with small average particle size and metal oxides (b2) with large average particle size, metal oxides (b1) can be filled in the gaps between metal oxides (b2), increasing the filling density and thus improving the thermal conductivity of the resulting thermoplastic resin composition.

[0105] Furthermore, for metal oxides (B), a small aspect ratio is preferred from the viewpoint of uniform heat conduction. Specifically, the aspect ratio is preferably less than 1.2, and more preferably less than 1.1.

[0106] The metal oxide (B) involved in this invention is preferably a water-resistant metal oxide. Preferably, the metal oxide (B) does not substantially contain metal hydroxides and their hydrates, or hydrates of metal oxides. Specifically, the content of metal hydroxides and their hydrates, and hydrates of metal oxides in 100% by mass of the total metal oxide (B) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

[0107] <Unmodified polyolefin wax (C)>

[0108] The unmodified polyolefin wax (C), which is one of the components included in the thermoplastic resin composition of the present invention, is a low molecular weight polymer. It can be any unmodified wax formed from polyolefins, such as polyethylene wax or polypropylene wax, and is not particularly limited. However, polyethylene wax or polypropylene wax is preferred, and polyethylene wax is more preferred.

[0109] It should be noted that the unmodified polyolefin wax (C) involved in this invention has not been oxidized or modified by unsaturated carboxylic acids, and is therefore unmodified.

[0110] Furthermore, the acid value of the unmodified polyolefin wax (C) of the present invention, as determined according to JIS K0070, is preferably 0.01 mg KOH / g or less, and more preferably 0 mg KOH / g.

[0111] Polyethylene-based waxes

[0112] The polyethylene wax used as the unmodified polyolefin wax (C) of this invention is a wax formed from a homopolymer of ethylene or a copolymer of ethylene and an α-olefin. The α-olefin is preferably an α-olefin with 3 to 10 carbon atoms, more preferably an α-olefin with 3 to 8 carbon atoms, and even more preferably 1-butene.

[0113] For the polyethylene-based waxes involved in this invention, the density, preferably measured according to the density gradient tube method of JIS K7112 (1999), is between 890 and 980 kg / m³. 3 More preferably, it is within the range of 895–975 kg / m³. 3 Within this range. If the density of the polyethylene wax is within this range, the dispersibility of the polyethylene wax in the thermoplastic resin composition is improved.

[0114] For the polyethylene-based waxes involved in this invention, the number-average molecular weight calculated based on standard polyethylene by gel permeation chromatography is preferably 700 to 4000, more preferably 1500 to 3800.

[0115] Polyethylene-based waxes with a number-average molecular weight (Mn) of 700 to 4000 can be more appropriately dispersed in the thermoplastic resin (A) when molding the thermoplastic resin composition of the present invention, and also contribute to the dispersibility of the metal oxide (B). Furthermore, the extrusion load during molding extrusion can be reduced. As a result, the productivity of molded articles can be further improved.

[0116] For the polyethylene-based waxes involved in this invention, the weight-average molecular weight (Mw) calculated based on standard polyethylene by gel permeation chromatography is preferably 1,000 to 9,000, more preferably 1,500 to 8,000, and even more preferably 2,000 to 7,000.

[0117] The melting point of the polyethylene-based wax involved in this invention is preferably 70–130°C, and more preferably 80–129°C.

[0118] The melting point of polyethylene wax was determined using a differential scanning calorimeter (DSC) in accordance with JIS K7121.

[0119] <Polypropylene Wax>

[0120] The polypropylene wax used as the unmodified polyolefin wax (C) of this invention is a wax formed from a homopolymer of propylene or a copolymer of propylene with ethylene or an α-olefin. The α-olefin is preferably an α-olefin with 4 to 10 carbon atoms, more preferably an α-olefin with 4 to 8 carbon atoms, and even more preferably 1-butene.

[0121] Thermoplastic Resin Compositions

[0122] The thermoplastic resin composition of the present invention is a composition comprising 10 to 50 parts by weight of the above-described thermoplastic resin (A), 50 to 90 parts by weight of the above-described metal oxide (B) [wherein the total amount of (A) + (B) is set to 100 parts by weight], and the above-described unmodified polyolefin wax (C) in the range of 0.1 to 20 parts by weight relative to the total amount of (A) + (B): 100 parts by weight.

[0123] The lower limit of the content of thermoplastic resin (A) in the thermoplastic resin composition of the present invention is preferably 12 parts by weight, more preferably 16 parts by weight, and even more preferably 20 parts by weight. If the content of thermoplastic resin (A) in the thermoplastic resin composition is a certain amount or more, conventional molding methods such as injection molding can be implemented.

[0124] The upper limit of the content of thermoplastic resin (A) is preferably 45 parts by weight, more preferably 40 parts by weight, and even more preferably 36 parts by weight.

[0125] If the content of thermoplastic resin (A) in the thermoplastic resin composition of the present invention is below a certain amount, the thermal conductivity of the obtained thermoplastic resin composition can be fully utilized, and the obtained molded body can feel weight and texture.

[0126] On the other hand, the lower limit of the content of metal oxide (B) is preferably 55 parts by mass, more preferably 60 parts by mass, and even more preferably 68 parts by mass.

[0127] In addition, the upper limit of the content of metal oxide (B) is preferably 88 parts by mass, more preferably 84 parts by mass, and even more preferably 80 parts by mass.

[0128] In applications requiring antibacterial and / or antiviral properties, the lower limit of the content of metal oxide (B) is preferably 70 parts by mass, more preferably 72 parts by mass, and even more preferably 74 parts by mass or more. Of course, the upper limit of the content of thermoplastic resin (A) is preferably 30 parts by mass, more preferably 28 parts by mass, and even more preferably 26 parts by mass or less.

[0129] By keeping the amounts of thermoplastic resin (A) and metal oxide (B) within the above range, it is possible to obtain molded articles with good moldability and antibacterial and / or antiviral properties.

[0130] When the total amount of thermoplastic resin (A) and metal oxide (B) is set to 100 parts by mass, the thermoplastic resin composition of the present invention contains 0.1 to 20 parts by mass of unmodified polyolefin wax (C). The lower limit of the content of unmodified polyolefin wax (C) is preferably 0.2 parts by mass, more preferably 0.4 parts by mass, and even more preferably 0.5 parts by mass.

[0131] Furthermore, the upper limit of the content of unmodified polyolefin wax (C) is preferably 15 parts by mass, more preferably 10 parts by mass, and even more preferably 5 parts by mass.

[0132] In the thermoplastic resin composition of the present invention, by including unmodified polyolefin wax (C) within the above-mentioned range, the molding torque during molding when obtaining the thermoplastic resin composition and during molding processing using the thermoplastic resin composition can be reduced, thereby improving the composability. In addition, since the melting temperature is lower than that of the thermoplastic resin (A), it functions as a lubricant, preventing wear on the screw and barrel.

[0133] On the other hand, since the thermoplastic resin composition of the present invention does not contain modified polyolefin wax, there is no concern about generating an unpleasant odor during molding and processing.

[0134] Furthermore, the molded articles obtained from the thermoplastic resin compositions of the present invention containing unmodified polyolefin wax (C) have a harder texture and a texture closer to that of ceramics compared to the molded articles obtained from compositions containing modified polyolefin wax, and there is no change in hydrophilicity. Therefore, there is no concern about the dissolution of metal oxides or the reduction of texture.

[0135] The specific gravity of the thermoplastic resin composition of the present invention is preferably in the range of 1.0 to 5.0. The lower limit of the specific gravity of the thermoplastic resin composition of the present invention is more preferably 1.2, further preferably 1.4, and particularly preferably 1.6. Furthermore, the upper limit of the specific gravity is more preferably 4.0, further preferably 3.0, and particularly preferably 2.5.

[0136] By ensuring the specific gravity falls within the aforementioned range, a molded object with better texture can be obtained.

[0137] The thermal conductivity of the thermoplastic resin composition of the present invention is preferably in the range of 0.5 to 5 W / mK. The lower limit of the thermal conductivity of the thermoplastic resin composition of the present invention is more preferably 0.6 W / mK, further preferably 0.65 W / mK, and particularly preferably 0.7 W / mK. Furthermore, the upper limit of the thermal conductivity is more preferably 4.5 W / mK, further preferably 4.0 W / mK, and particularly preferably 3.6 W / mK.

[0138] By ensuring that the thermal conductivity meets the above-mentioned range, molded objects such as containers can be obtained that feel cool to the touch and have a better texture.

[0139] For the thermoplastic resin composition of the present invention, it is preferable to use Escherichia coli or Staphylococcus aureus with an antibacterial activity value of 2.0 or higher, and more preferably, it is preferable to use Escherichia coli and Staphylococcus aureus with an antibacterial activity value of 2.0 or higher. The antibacterial activity value of the thermoplastic resin composition of the present invention can be increased, for example, by increasing the content of metal oxide (B) (e.g., magnesium oxide). It should be noted that if the antibacterial activity value is 2.0 or higher, it can be considered to have an antibacterial effect. The higher the antibacterial activity value, the higher the antibacterial effect, and therefore it is preferred, and there is no particular upper limit.

[0140] The antibacterial activity value in this invention is an index value obtained according to the test method in JIS Z 2801:2012 "Membrane tightness method".

[0141] For the thermoplastic resin composition of the present invention, it is preferable to use a feline calicivirus with an antiviral activity value of 2.0 or higher. It should be noted that an antiviral activity value of 2.0 or higher is considered to indicate an antiviral effect. A higher antiviral activity value indicates a higher antiviral effect, and is therefore preferred; however, there is no particular upper limit.

[0142] The antiviral activity value in this invention is an index value obtained according to the test method in ISO 21702:2019 "Determination of antiviral activity of plastics and other non-porous surfaces".

[0143] The thermoplastic resin composition of the present invention may contain a fibrous filler (D) in addition to the unmodified polyolefin wax (C).

[0144] <Fibrous filler (D)>

[0145] The fibrous filler (D) involved in this invention is a fibrous filler, specifically including glass fiber, carbon fiber, magnesium sulfate fiber, polyester fiber, nylon fiber, kenaf fiber, bamboo fiber, jute fiber, and inorganic crystalline whisker fiber. Among these, glass fiber and carbon fiber are preferred.

[0146] When the thermoplastic resin composition of the present invention contains a fibrous filler (D), the mechanical properties such as the strength of the resulting molded article are improved.

[0147] When the thermoplastic resin composition of the present invention contains a fibrous filler (D), the fibrous filler (D) is present in the range of 0.1 to 20 parts by mass relative to 100 parts by mass of the total mass of the thermoplastic resin (A) and the metal oxide (B). The lower limit of the content of the fibrous filler (D) is preferably 0.2 parts by mass, more preferably 0.3 parts by mass. Furthermore, the upper limit of the content of the fibrous filler (D) is preferably 15 parts by mass, more preferably 10 parts by mass, and even more preferably 8 parts by mass.

[0148] The thermoplastic resin composition of the present invention may contain fillers other than fibrous filler (D) to a extent that does not impair the effects of the present invention. Examples of such fillers include inorganic fillers such as talc, mica, calcium carbonate, ammonium phosphate, silicates, carbonates, and carbon black; and organic fillers such as wood flour, cellulose, rice flour, starch, and corn starch.

[0149] In addition to the fibrous filler (D) described above, the thermoplastic resin composition of the present invention may also contain various known additives, such as plasticizers, lubricants, antioxidants, ultraviolet absorbers, heat stabilizers, pigments, pigment masterbatches, dyes, antistatic agents, flame retardants, coupling agents, and dispersants, depending on the application and without prejudice to the purpose of the present invention.

[0150] <Method for manufacturing thermoplastic resin compositions>

[0151] The thermoplastic resin composition of the present invention can be obtained by mixing the above components using a dry mixer, Henschel mixer, Banbury mixer, kneader, etc., or by melt mixing using a single-screw extruder, twin-screw extruder, high-speed twin-screw extruder, etc.

[0152] <Molded Body>

[0153] The thermoplastic resin composition of the present invention exhibits excellent moldability and can therefore be used in various molding methods. Specific examples of molded articles obtained from the thermoplastic resin composition of the present invention include injection molded articles, foamed articles, injection foamed articles, extruded articles, hollow articles, vacuum-formed articles, calendered articles, stretch films, and blown films.

[0154] More specifically, examples include containers for holding food, forks, knives, spoons, plates, small teapots, teacups, and other tableware; wine vessels such as wine jugs or bottles; and cutlery rests such as chopstick rests. Considering their ease of injection molding, the ability to easily feel the temperature of their contents, and the sense of weight, they are very useful as alternatives to ceramic tableware, wine vessels, containers, and cutlery. Furthermore, their use can be extended to other applications of ceramics, such as lampshades, vases, and other everyday items; housings and structural materials for specific audio speakers (high-end speakers, etc.); bathroom products such as washbasins and toilets; and vases and flowerpots for holding plants. Beyond its applications in ceramics, its weight and stability can be effectively utilized to expand into various uses, such as model making and toys (e.g., plastic models), furniture (e.g., tables, chairs), home appliances (e.g., refrigerators, rice cookers, vacuum cleaners), musical instruments (e.g., piano keyboards), construction materials (e.g., tiles, artificial marble substitutes), and clothing (e.g., buttons). Furthermore, its temperature sensitivity and moldability make it potentially suitable as filaments for 3D printers.

[0155] In addition to the molded articles of the present invention, various containers such as bottles and kettles, steering wheels, gear shift levers, door handles, spherical door handles, various switches, railings, mice, keyboards, controllers, decorative accessories, stationery, smartphone covers, tablet protective cases, personal computer / tablet shells, book covers, etc., which effectively utilize features such as design, stability, antibacterial properties, and tactile feel, can be used in everyday situations involving hand contact.

[0156] Among containers, preferred examples are containers for beauty-related products such as cosmetics (lotions, creams, etc.), detergents (including shower gels, etc.), and conditioners, whose properties tend to have a high impact on the value of the product. More specifically, containers in the shape of lidded containers (including vacuum containers, etc.), small cosmetic boxes, cosmetic palettes, and bottles can be cited.

[0157] In such applications, containers made of lightweight and impact-resistant plastics such as polyolefins have been widely used in recent years. However, these are not suitable materials for conveying a sense of luxury in terms of visual appeal and tactile feel (including thermal conductivity and weight). Containers such as ceramics are suitable for conveying a sense of luxury, but they have significant drawbacks such as limitations in design and mass production, and low impact resistance.

[0158] The container of the present invention can be molded using the same methods as conventional plastic products. Therefore, it not only has excellent productivity and design, but also has superior impact resistance compared to ceramics, and has the same weight and thermal conductivity as ceramics. Thus, it can be considered suitable for the aforementioned applications.

[0159] Furthermore, the molded articles obtained from the thermoplastic resin composition of the present invention are also useful as heat dissipation components for applications requiring high thermal conductivity. For example, they are very useful as heat dissipation components such as heat sinks in various electronic devices such as electronic components requiring high thermal conductivity, laptops, and mobile devices. In addition, if the thermoplastic resin composition of the present invention is applied to part or all of the housing of various electronic devices such as laptops and mobile devices and used in combination with heat sinks, it is expected that the heat dissipation performance of electronic devices can be further improved. Furthermore, the thermoplastic resin composition of the present invention can be used in part of the housing of various electronic devices such as laptops and mobile devices, while materials with reduced metal oxide content or materials without metal oxides are used in other parts, such as parts that are frequently touched by hands during operation, thereby creating a housing that can reduce the possibility of low-temperature burns during prolonged operation. Such a housing can be manufactured, for example, by providing multiple resin injection gates on a mold for molding the housing and injecting resins of different compositions into each gate.

[0160] As for other applications, its excellent thermal conductivity, flexibility in shaping during molding, and high impact strength make it useful as a substitute for metal casings. For example, it can be expected to be used in the casings and straps of clocks and watches, furniture parts (such as metal handles), and exterior decorative materials for household appliances such as washing machines and refrigerators.

[0161] Example

[0162] The present invention will be described in more detail below with reference to embodiments, but the present invention is not limited to the following embodiments, as long as they do not depart from its spirit. The materials used in the embodiments are described below. The methods for evaluating the properties of each material are described later.

[0163] The following shows the thermoplastic resin (A) used in the examples and comparative examples.

[0164] (1) Thermoplastic resin (A)

[0165] (1-1) Propylene-based polymers (A2-1): Propylene-ethylene block copolymer (manufactured by Prime Polymer Co., Ltd., trade name X860, MFR (230℃, load 2.16kg) = 60g / 10min, density = 900kg / m³) 3 Xylene soluble fraction at 25°C = 24% by mass; intrinsic viscosity of xylene soluble fraction at 25°C [η] = 2.5 dl / g; ethylene content of xylene soluble fraction at 25°C = 30% by mass.

[0166] (1-2) Propylene-based polymers (A2-2): Propylene-ethylene block copolymer (manufactured by Prime Polymer Co., Ltd., trade name J-6083HP, MFR (230℃, load 2.16kg) = 60g / 10min, density = 900kg / m³) 3 ).

[0167] (1-3) Propylene polymers (A2-3): Short fiber glass-reinforced polypropylene (manufactured by Prime Polymer Co., Ltd., Prime Polypro (registered trademark) V7100, glass fiber content = 20wt%, MFR (230℃, load 2.16kg) = 18g / 10min, density = 1030kg / m³ 3 ).

[0168] (1-4) Ethylene-based polymers (A1-1): High-density polyethylene (manufactured by Prime Polymer Co., Ltd., HI-ZEX (registered trademark), trade name 1300J, MFR (190℃, load 2.16kg) = 13g / 10min, density = 967kg / m³ 3 ).

[0169] (1-5) Ethylene-based polymers (A1-2): High-density polyethylene (manufactured by Prime Polymer Co., Ltd., HI-ZEX (registered trademark), trade name 1700J), MFR (190℃, load 2.16kg) = 16g / 10min, MFR (230℃, load 2.16kg) = 28g / 10min, density = 967kg / m³ 3 ).

[0170] (1-6) Ethylene-based polymers (A1-3): Ethylene-1-butene copolymer (manufactured by Mitsui Chemicals, Ltd., TAFMER (registered trademark), trade name A-35070S, MFR (190℃, 2.16kg load) = 35g / 10min, MFR (230℃, 2.16kg load) = 65g / 10min, density = 870kg / m³ 3 ).

[0171] (1-7) Propylene polymers (A2-4): Propylene homopolymer (manufactured by Prime Polymer Co., Ltd., trade name J13B, MFR (230℃, load 2.16kg) = 200g / 10min, density = 890kg / m³) 3 ).

[0172] (1-8) 4-Methyl-1-pentene polymers (A4-1): 4-Methyl-1-pentene-propylene copolymers are copolymers manufactured by the methods described below.

[0173] (1-9) ABS Resin (A5-1): ABS resin (manufactured by NIPPON A&L INC., trade name GA-704, MVR (220℃, load 10kg) = 62cm) 3 MFR (230℃, 5kg load) = 39.8g / 10min, MFR (230℃, 2.16kg load) = 13g / 10min, density 1040kg / m³ 3 )

[0174] [Method for manufacturing 4-methyl-1-pentene polymer (A4-1)]

[0175] In a 1.5L SUS autoclave equipped with a stirring blade and fully nitrogen-purified, 300 ml of n-hexane (dried on activated alumina under a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were added at 23°C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was then added to the autoclave, and the stirrer was turned.

[0176] Next, the autoclave is heated to an internal temperature of 60°C and pressurized with propylene at a total pressure (gauge pressure) of 0.40 MPa.

[0177] Next, 0.34 ml of a pre-prepared toluene solution containing 1 mmol of methylaluminoxane (calculated as Al) and 0.01 mmol of diphenylmethylene (1-ethyl-3-tert-butylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconia dichloride was pressurized into the autoclave to initiate the polymerization reaction. The temperature of the autoclave was maintained at 60°C during the polymerization reaction.

[0178] Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave using nitrogen to stop the polymerization reaction. The autoclave was then depressurized to atmospheric pressure. After depressurization, acetone was added to the reaction solution while stirring to obtain the polymerization product containing the solvent.

[0179] Next, the obtained polymerization product containing solvent was dried at 100°C for 12 hours under reduced pressure to obtain 36.9 g of powdered 4-methyl-1-pentene polymer (A4-1).

[0180] The 4-methyl-1-pentene polymer (A4-1) contains 72.5 mol% 4-methyl-1-pentene and 27.5 mol% propylene. Furthermore, the physical properties of the 4-methyl-1-pentene polymer (A4-1) are as follows.

[0181] Density is 839 kg / m³ 3 The intrinsic viscosity [η] is 1.5 dl / g, the weight-average molecular weight (Mw) is 337,000, the molecular weight distribution (Mw / Mn) is 2.1, the melt flow rate (MFR; 230℃, 2.16 kg load) is 11 g / 10 min, and the melting point (Tm) was not observed. Additionally, the peak temperature of tanδ is 30℃, and the peak value is 2.78.

[0182] The MFR and density of each of the above thermoplastic resins (A) were determined by the following methods.

[0183] [Mel flow rate (MFR) (g / 10 min)]

[0184] According to ASTM D1238, the test shall be conducted at a temperature of 190°C and a load of 2.16 kg, at a temperature of 230°C and a load of 2.16 kg, or at a temperature of 230°C and a load of 5 kg.

[0185] 〔density〕

[0186] The determination was carried out in accordance with JIS K 7112.

[0187] [Composition of 4-methyl-1-pentene polymer (A4-1)]

[0188] The content (mol%) of each structural unit (4-methyl-1-pentene and α-olefin) in the 4-methyl-1-pentene polymer (A4-1) is used to... 13 The determination was performed using C-NMR.

[0189] • Measurement apparatus: Nuclear magnetic resonance spectrometer (ECP500 type, manufactured by NEC Corporation)

[0190] • Observation kernel: 13 C(125MHz)

[0191] • Sequence: Single-pulse proton decoupling

[0192] • Pulse width: 4.7 μs (45° pulse)

[0193] • Repetition time: 5.5 seconds

[0194] • Cumulative number of times: 10,000 or more

[0195] • Solvent: o-dichlorobenzene / deuterated benzene (capacity ratio: 80 / 20) mixed solvent

[0196] • Sample concentration: 55 mg / 0.6 mL

[0197] • Measurement temperature: 120℃

[0198] • Reference value for chemical shift: 27.50 ppm

[0199] Intrinsic viscosity [η] of 4-methyl-1-pentene polymer (A4-1)

[0200] The intrinsic viscosity [η] was measured at 135 °C in decahydronaphthalene solvent using an Ubbelohde viscometer as the measuring device.

[0201] Approximately 20 mg of a specific 4-methyl-1-pentene copolymer was dissolved in 25 ml of decahydronaphthalene, and the specific viscosity ηsp was measured using an Ubbelohde viscometer in an oil bath at 135 °C. The decahydronaphthalene solution was diluted by adding 5 ml of decahydronaphthalene, and the specific viscosity ηsp was measured in the same manner as described above. This dilution was repeated twice more, and the value of ηsp / C, extrapolated to 0 from the concentration (C), was taken as the intrinsic viscosity [η] (unit: dl / g) (see Equation 1 below).

[0202] [η]=lim(ηsp / C)(C→0)···Equation 1

[0203] [Weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of 4-methyl-1-pentene polymers (A4-1)]

[0204] The weight-average molecular weight (Mw) and the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), were calculated using the standard polystyrene conversion method of gel permeation chromatography (GPC).

[0205] -condition-

[0206] Measuring apparatus: GPC (ALC / GPC 150-C plus type, differential refractometer detector integrated type, Waters)

[0207] Columns: Connect two GMH6-HT (manufactured by Tosoh Corporation) and two GMH6-HTL (manufactured by Tosoh Corporation) in series.

[0208] Eluent: o-dichlorobenzene

[0209] Column temperature: 140℃

[0210] Flow rate: 1.0 mL / min

[0211] [Melting point (Tm) of 4-methyl-1-pentene polymer (A4-1)]

[0212] The melting point (Tm) was determined using a differential scanning calorimeter (DSC220C, manufactured by Seiko Instruments Inc.). Approximately 5 mg of the polymer was sealed in an aluminum measuring dish and heated from room temperature to 200°C at a rate of 10°C / min. To ensure complete melting of the polymer, it was held at 200°C for 5 minutes, followed by cooling to -50°C at a rate of 10°C / min. After being placed at -50°C for 5 minutes, a second heating to 200°C was performed at a rate of 10°C / min. The peak temperature (°C) of this second heating was taken as the melting point (Tm) of the polymer. It should be noted that in cases where multiple peaks were detected, the peak detected at the highest temperature was used.

[0213] [Dynamic viscoelasticity of 4-methyl-1-pentene polymers (A4-1)]

[0214] In the determination of dynamic viscoelasticity, a 3 mm thick pressurized sheet formed from the resin to be tested was used as the test sample. Strips of 45 mm × 10 mm × 3 mm were then cut out for the dynamic viscoelasticity determination. Using an ANTONPaar MCR301, the temperature dependence of dynamic viscoelasticity from -40 to 150 °C was measured at a frequency of 10 rad / s (1.6 Hz). Within the range of 0–40 °C, the temperature at which the loss tangent (tanδ) originating from the glass transition temperature reaches its peak (maximum value) (hereinafter referred to as the "peak temperature") and the value of the loss tangent (tanδ) at this point were determined.

[0215] The following shows the metal oxide (B) used in the examples and comparative examples.

[0216] (2) Metal oxides (B)

[0217] (2-1) Magnesium oxide (B-1): MgO (manufactured by Kyowa Chemical Industry Co., Ltd., PYROKISUMA 5301, average particle size = 2μm).

[0218] (2-2) Magnesium oxide (B-2): MgO (manufactured by Kyowa Chemical Industry Co., Ltd., PYROKISUMA 3320, average particle size = 20 μm).

[0219] (2-3) Magnesium oxide (B-3): Magnesium oxide that has undergone the treatment described below is used.

[0220] MgO (DENMAG KMAO-H produced by Tateho Chemical Industries Co., Ltd. (average particle size = 45-355 μm)) was sieved using a 180-250 mesh sieve to obtain magnesium oxide (B-3) with an average particle size of about 60-80 μm.

[0221] The following shows the unmodified polyolefin wax (C) used in the examples and comparative examples.

[0222] (3) Unmodified polyolefin waxes (C)

[0223] (3-1) Unmodified polyolefin wax (C-1): Ethylene-1-butene copolymer (manufactured by Mitsui Chemicals, Ltd., trade name EXCEREX 30050B, density = 907 kg / m³) 3 Acid value = 0 mg KOH / g, melting point = 91℃, weight-average molecular weight = 5100, molecular weight distribution Mw / Mn = 2.6).

[0224] (4) Modified polyolefin waxes

[0225] (4-1) Modified polyolefin wax: Modified polyolefin polymer (manufactured by Mitsui Chemicals Co., Ltd., trade name EXCEREX15341PA, density = 930 kg / m³) 3 Acid value = 14 mg KOH / g, melting point = 89℃).

[0226] The physical properties of the thermoplastic resin compositions obtained in the examples and comparative examples were determined by the following methods.

[0227] 〔proportion〕

[0228] The specific gravity was determined by comparing it with the density of water at 4°C using the water displacement method.

[0229] [Mel flow rate (MFR) (g / 10 min)]

[0230] According to ASTM D1238, the test shall be conducted at a temperature of 230°C and a load of 2.16 kg, or at a temperature of 230°C and a load of 5 kg.

[0231] [Pencil Hardness]

[0232] The hardness of the pencil was determined using a test load of 750g.

[0233] Thermal conductivity (W / m·K)

[0234] Thermal conductivity was determined using a steady-state heat flow meter method. Specifically, a ULVAC-RIKO, Inc. measuring instrument GH-1 was used, and the measurement was performed at 30°C according to ASTM E1530.

[0235] [Determination of flexural temperature under load (°C)]

[0236] According to ISO 75-2 Method A, the test specimen (2mm × 10mm × 80mm) was used, and the test was conducted under the following conditions: heating rate of 120℃ / hour, test start temperature of 35℃, and bending stress of 1.8MPaG. The HDT was measured using a fully automatic HDT testing machine model 6A-2 (manufactured by Toyo Seiki Co., Ltd.).

[0237] [Water absorption rate (wt%)]

[0238] The water absorption rate was measured at 23℃ for 24 hours.

[0239] [Antibacterial activity value (-)]

[0240] The test method shall be carried out in accordance with the test method in JIS Z 2801:2012 "Membrane Tightness Method", and the antibacterial activity value shall be calculated by the following formula.

[0241] "Antibacterial activity value" = "Common logarithmic value of viable bacteria count in blank samples 24 hours after inoculation with Escherichia coli or Staphylococcus aureus" - "Common logarithmic value of viable bacteria count in test strips 24 hours after inoculation with Escherichia coli or Staphylococcus aureus"

[0242] The test strains used in this experiment are shown below.

[0243] Antibacterial activity value (Escherichia coli): Escherichia coli NBRC 3972

[0244] Antibacterial activity value (Staphylococcus aureus): Staphylococcus aureus NBRC 12732

[0245] [Antiviral activity value (-)]

[0246] The antiviral activity value of the thermoplastic resin composition was determined according to the test method in ISO 21702:2019.

[0247] Specifically, a 50 mm square sample was placed in a sterile Petri dish, and 0.4 mL of virus solution was inoculated onto the sample. Then, a coating was placed over the sample. After capping, the Petri dish was inoculated with virus for 24 hours at a temperature of 25°C and humidity above 90%. The virus was recovered from the sample, and the viral titer was determined using the plaque assay. The antiviral activity value was calculated using the following formula.

[0248] "Antiviral activity value" = "Common logarithmic value of viral infection titer of blank sample 24 hours after inoculation [Ut]" - "Common logarithmic value of test strip 24 hours after inoculation [At]"

[0249] The following shows the virus used in this experiment.

[0250] Feline calicivirus: ATCC VR-782

[0251] (1) Antibacterial properties (water resistance category 0 and light resistance category 0: conditions without light resistance and water resistance pretreatment)

[0252] For water resistance category 0 and light resistance category 0, the "Antibacterial Products Technical Association Test Method Continuous Test Method (2020 Edition) (1) Water Resistance Test" and the "Antibacterial Products Technical Association Test Method Continuous Test Method (2020 Edition)" were not implemented.

[0253] (2) The water resistance and light resistance of the pretreated samples described in the "Light Resistance Test" were subjected to the aforementioned test based on the "membrane sealing method" to calculate the antibacterial activity value.

[0254] It should be noted that, assuming that the performance of products with antibacterial or antiviral properties during pretreatment may be reduced due to contact with water or exposure to light, the samples are treated under the test conditions specified in each category (water temperature, immersion time, or irradiation time by a light source).

[0255] (2) Durability of antibacterial properties (water resistance category 1 and water resistance category 2)

[0256] For water resistance categories 1 and 2, samples pretreated according to the "Antibacterial Products Technical Association Test Method Continuity Test Method (2020 Edition) (1) Water Resistance Test" were used to perform the aforementioned test based on the "membrane tightness method" and calculate the antibacterial activity value.

[0257] (3) Durability of antibacterial activity (lightfastness category 1 and lightfastness category 2)

[0258] For lightfastness categories 1 and 2, samples pretreated according to the "Antibacterial Products Technical Association Test Method Continuity Test Method (2020 Edition) (2) Lightfastness Test" were used to perform the aforementioned test based on the "membrane tightness method" and calculate the antibacterial activity value.

[0259] [Example 1]

[0260] A thermoplastic resin composition was obtained by mixing 30 parts by weight of a propylene polymer (A2-1), 70 parts by weight of magnesium oxide (B-1), and 0.6 parts by weight of unmodified polyolefin wax (C-1) at 200°C and 15–35 rpm using a mixing apparatus (a benchtop kneader manufactured by Irie & Co.). The granules of the obtained thermoplastic resin composition were then pressed into pressurized sheets at 200°C using a manual hydraulic heating and pressurizing device (manufactured by Imoto Manufacturing Co., Ltd.), yielding samples for physical property testing. The physical properties of the obtained sheets were measured using the methods described above.

[0261] The results are shown in Table 1.

[0262] [Example 2]

[0263] As raw materials for the thermoplastic resin composition, 23 parts by weight of propylene polymer (A2-2), 2.0 parts by weight of ethylene polymer (A1-3), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, samples for physical property testing were prepared in the same manner as in Example 1, and the physical properties were measured using the methods described above. Furthermore, antibacterial persistence tests in water resistance category 0 and light resistance category 0 were performed using the methods described above.

[0264] The results are shown in Table 1.

[0265] In addition, antibacterial and antiviral persistence tests were conducted in water resistance category 1, water resistance category 2, light resistance category 1, and light resistance category 2 using the methods described above.

[0266] The results of the antimicrobial persistence tests in water resistance categories 1 and 2 and light resistance categories 1 and 2 are shown in Table 2, and the results of the antiviral persistence tests in water resistance categories 1 and 2 and light resistance categories 1 and 2 are shown in Table 3.

[0267] [Example 3]

[0268] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 23 parts by mass of propylene polymer (A2-2), 2.0 parts by mass of ethylene polymer (A1-3), 15 parts by mass of magnesium oxide (B-1), 60 parts by mass of magnesium oxide (B-2), and 0.6 parts by mass of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0269] The results are shown in Table 1.

[0270] [Example 4]

[0271] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 23 parts by mass of propylene polymer (A2-2), 2.0 parts by mass of ethylene polymer (A1-3), 22.5 parts by mass of magnesium oxide (B-1), 52.5 parts by mass of magnesium oxide (B-2), and 0.6 parts by mass of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0272] The results are shown in Table 1.

[0273] [Example 5]

[0274] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 24.5 parts by weight of propylene polymer (A2-2), 0.5 parts by weight of ethylene polymer (A1-3), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0275] The results are shown in Table 1.

[0276] [Example 6]

[0277] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 29.5 parts by weight of propylene polymer (A2-2), 0.5 parts by weight of ethylene polymer (A1-3), 70 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0278] The results are shown in Table 1.

[0279] [Example 7]

[0280] As raw materials for the thermoplastic resin composition, 34.5 parts by weight of propylene polymer (A2-2), 0.5 parts by weight of ethylene polymer (A1-3), 65 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, samples for physical property testing were prepared in the same manner as in Example 1, and the physical properties were measured using the methods described above. Furthermore, antibacterial persistence tests in water resistance category 0 and light resistance category 0 were performed using the methods described above.

[0281] The results are shown in Table 1.

[0282] [Example 8]

[0283] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 23 parts by mass of propylene polymer (A2-3), 2.0 parts by mass of ethylene polymer (A1-3), 75 parts by mass of magnesium oxide (B-2), and 0.6 parts by mass of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0284] The results are shown in Table 1.

[0285] It should be noted that the propylene polymer (A2-3) contains 20% by mass of glass fiber, as described above. The blending ratio when the total amount of the propylene polymer (A2-3) excluding the glass fiber (PP portion) and magnesium oxide (B-2) is set at 100 parts by mass is as follows: 19.3 parts by mass of the PP portion of the propylene polymer (A2-3), 2.1 parts by mass of the ethylene polymer (A1-3), 78.6 parts by mass of magnesium oxide (B-2), 0.6 parts by mass of unmodified polyolefin wax (C-1), and 4.8 parts by mass of the glass fiber portion of the propylene polymer (A2-3).

[0286] [Example 9]

[0287] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 11.5 parts by weight of propylene polymer (A2-2), 11.5 parts by weight of propylene polymer (A2-3), 2.0 parts by weight of ethylene polymer (A1-3), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0288] The results are shown in Table 1.

[0289] It should be noted that the propylene polymer (A2-3) contains 20% by mass of glass fiber, as described above. The blending ratio when the total amount of the propylene polymer (A2-3) excluding the glass fiber (PP portion), the propylene polymer (A2-2), and the magnesium oxide (B-2) is set at 100 parts by mass is as follows: 11.8 parts by mass of propylene polymer (A2-2), 9.4 parts by mass of the PP portion of the propylene polymer (A2-3), 2.0 parts by mass of the ethylene polymer (A1-3), 76.8 parts by mass of magnesium oxide (B-2), 0.6 parts by mass of unmodified polyolefin wax (C-1), and 2.4 parts by mass of the glass fiber portion of the propylene polymer (A2-3).

[0290] [Example 10]

[0291] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 15.3 parts by weight of propylene polymer (A2-2), 7.7 parts by weight of propylene polymer (A2-3), 2.0 parts by weight of ethylene polymer (A1-3), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the method described above.

[0292] The results are shown in Table 1.

[0293] It should be noted that the propylene polymer (A2-3) contains 20% by mass of glass fiber, as described above. The blending ratio when the total mass of the propylene polymer (A2-3) excluding the glass fiber (PP portion), the propylene polymer (A2-2), and the magnesium oxide (B-2) is set at 100 parts by mass is as follows: 15.5 parts by mass of propylene polymer (A2-2), 6.3 parts by mass of the PP portion of the propylene polymer (A2-3), 2.0 parts by mass of the ethylene polymer (A1-3), 76.2 parts by mass of magnesium oxide (B-2), 0.6 parts by mass of unmodified polyolefin wax (C-1), and 1.6 parts by mass of the glass fiber portion of the propylene polymer (A2-3).

[0294] [Example 11]

[0295] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 25 parts by weight of ethylene polymer (A1-1), 22.5 parts by weight of magnesium oxide (B-1), 52.5 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0296] The results are shown in Table 1.

[0297] [Example 12]

[0298] As raw materials for the thermoplastic resin composition, 25 parts by weight of ethylene polymer (A1-1), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the method described above.

[0299] The results are shown in Table 1.

[0300] [Example 13]

[0301] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 33 parts by mass of ethylene polymer (A1-1), 2.0 parts by mass of ethylene polymer (A1-3), 65 parts by mass of magnesium oxide (B-2), and 0.6 parts by mass of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0302] The results are shown in Table 1.

[0303] [Example 14]

[0304] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 18 parts by mass of ethylene polymer (A1-1), 2.0 parts by mass of ethylene polymer (A1-3), 80 parts by mass of magnesium oxide (B-2), and 0.6 parts by mass of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0305] The results are shown in Table 1.

[0306] [Example 15]

[0307] As raw materials for the thermoplastic resin composition, 25 parts by weight of ethylene polymer (A1-2), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the method described above.

[0308] The results are shown in Table 1.

[0309] [Example 16]

[0310] As raw materials for the thermoplastic resin composition, 23 parts by weight of ethylene polymer (A1-2), 2.0 parts by weight of ethylene polymer (A1-3), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, samples for physical property testing were prepared in the same manner as in Example 1, and the physical properties were measured using the methods described above. Furthermore, antibacterial persistence tests in water resistance category 0 and light resistance category 0 were performed using the methods described above.

[0311] The results are shown in Table 1.

[0312] [Example 17]

[0313] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 23 parts by mass of ethylene polymer (A1-2), 2.0 parts by mass of ethylene polymer (A1-3), 75 parts by mass of magnesium oxide (B-2), 0.6 parts by mass of unmodified polyolefin wax (C-1), and 1.0 parts by mass of carbon black were used to prepare samples for physical property testing in the same manner as in Example 1, and the physical properties were measured by the methods described above.

[0314] The results are shown in Table 1.

[0315] [Example 18]

[0316] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 28 parts by mass of propylene polymer (A2-2), 2.0 parts by mass of ethylene polymer (A1-3), 70 parts by mass of magnesium oxide (B-3), and 0.6 parts by mass of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0317] The results are shown in Table 1.

[0318] [Example 19]

[0319] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 28 parts by weight of propylene polymer (A2-2), 2.0 parts by weight of ethylene polymer (A1-3), 70 parts by weight of magnesium oxide (B-3), and 1 part by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0320] The results are shown in Table 1.

[0321] [Example 20]

[0322] As raw materials for the thermoplastic resin composition, 28 parts by weight of propylene polymer (A2-2), 2.0 parts by weight of ethylene polymer (A1-3), 70 parts by weight of magnesium oxide (B-3), and 2 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0323] The results are shown in Table 1.

[0324] [Example 21]

[0325] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 23 parts by mass of propylene polymer (A2-2), 2.0 parts by mass of ethylene polymer (A1-3), 75 parts by mass of magnesium oxide (B-3), and 0.6 parts by mass of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0326] The results are shown in Table 1.

[0327] [Example 22]

[0328] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 14 parts by weight of propylene polymer (A2-2), 14 parts by weight of propylene polymer (A2-4), 2.0 parts by weight of ethylene polymer (A1-3), 70 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0329] The results are shown in Table 1.

[0330] [Example 23]

[0331] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 18.7 parts by weight of propylene polymer (A2-2), 9.3 parts by weight of propylene polymer (A2-3), 2.0 parts by weight of ethylene polymer (A1-3), 70 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0332] The results are shown in Table 1.

[0333] It should be noted that the propylene polymer (A2-3) contains 20% by mass of glass fiber, as described above. The blending ratio when the total amount of the propylene polymer (A2-3) excluding the glass fiber (PP portion), the propylene polymer (A2-2), and the magnesium oxide (B-2) is set at 100 parts by mass is as follows: 19.1 parts by mass of propylene polymer (A2-2), 7.6 parts by mass of the PP portion of the propylene polymer (A2-3), 2.0 parts by mass of the ethylene polymer (A1-3), 71.3 parts by mass of magnesium oxide (B-2), 0.6 parts by mass of unmodified polyolefin wax (C-1), and 1.9 parts by mass of the glass fiber portion of the propylene polymer (A2-3).

[0334] [Example 24]

[0335] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 11.5 parts by weight of propylene polymer (A2-3), 11.5 parts by weight of propylene polymer (A2-4), 2.0 parts by weight of ethylene polymer (A1-3), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0336] The results are shown in Table 1.

[0337] It should be noted that the propylene polymer (A2-3) contains 20% by mass of glass fiber as described above. The blending ratio when the total amount of the propylene polymer (A2-3) excluding the glass fiber (PP portion), the propylene polymer (A2-4), and the magnesium oxide (B-2) is set at 100 parts by mass is as follows: 9.4 parts by mass of the PP portion of the propylene polymer (A2-3), 11.8 parts by mass of the propylene polymer (A2-4), 2.0 parts by mass of the ethylene polymer (A1-3), 76.8 parts by mass of the magnesium oxide (B-2), 0.6 parts by mass of the unmodified polyolefin wax (C-1), and 2.4 parts by mass of the glass fiber portion of the propylene polymer (A2-3).

[0338] [Example 25]

[0339] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 14 parts by weight of propylene polymer (A2-3), 14 parts by weight of propylene polymer (A2-4), 2.0 parts by weight of ethylene polymer (A1-3), 70 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0340] The results are shown in Table 1.

[0341] It should be noted that the propylene polymer (A2-3) contains 20% by mass of glass fiber, as described above. The blending ratio when the total mass of the propylene polymer (A2-3) excluding the glass fiber (PP portion), the propylene polymer (A2-4), and the magnesium oxide (B-2) is set at 100 parts by mass is as follows: 11.5 parts by mass of the PP portion of the propylene polymer (A2-3), 14.4 parts by mass of the propylene polymer (A2-4), 2.1 parts by mass of the ethylene polymer (A1-3), 72 parts by mass of the magnesium oxide (B-2), 0.6 parts by mass of the unmodified polyolefin wax (C-1), and 2.9 parts by mass of the glass fiber portion of the propylene polymer (A2-3).

[0342] [Example 26]

[0343] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 14 parts by weight of propylene polymer (A2-3), 14 parts by weight of propylene polymer (A2-4), 2.0 parts by weight of ethylene polymer (A1-3), 70 parts by weight of magnesium oxide (B-2), and 1.0 parts by weight of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0344] The results are shown in Table 1.

[0345] It should be noted that the propylene polymer (A2-3) contains 20% by mass of glass fiber, as described above. The blending ratio when the total mass of the propylene polymer (A2-3) excluding the glass fiber (PP portion), the propylene polymer (A2-4), and the magnesium oxide (B-2) is set at 100 parts by mass is as follows: 11.5 parts by mass of the PP portion of the propylene polymer (A2-3), 14.4 parts by mass of the propylene polymer (A2-4), 2.1 parts by mass of the ethylene polymer (A1-3), 72 parts by mass of the magnesium oxide (B-2), 1.0 part by mass of the unmodified polyolefin wax (C-1), and 2.9 parts by mass of the glass fiber portion of the propylene polymer (A2-3).

[0346] [Example 27]

[0347] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 33 parts by mass of ethylene polymer (A1-2), 2.0 parts by mass of ethylene polymer (A1-3), 65 parts by mass of magnesium oxide (B-2), and 0.6 parts by mass of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the methods described above.

[0348] The results are shown in Table 1.

[0349] [Example 28]

[0350] As raw materials for the thermoplastic resin composition, 35.0 parts by weight of 4-methyl-1-pentene polymer (A4-1), 65 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0351] The results are shown in Table 1.

[0352] [Example 29]

[0353] As raw materials for the thermoplastic resin composition, 30 parts by weight of 4-methyl-1-pentene polymer (A4-1), 70 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, the same procedures were followed as in Example 1 to prepare samples for property testing. Furthermore, antibacterial persistence tests in water resistance category 0 and light resistance category 0 were performed using the methods described above.

[0354] The results are shown in Table 1.

[0355] [Example 30]

[0356] As raw materials for the thermoplastic resin composition, 25 parts by weight of 4-methyl-1-pentene polymer (A4-1), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, the same procedure was followed as in Example 1 to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0357] The results are shown in Table 1.

[0358] [Example 31]

[0359] As raw materials for the thermoplastic resin composition, 35 parts by weight of ABS resin (A5-1), 65 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the method described above.

[0360] The results are shown in Table 1.

[0361] [Example 32]

[0362] As raw materials for the thermoplastic resin composition, 30 parts by weight of ABS resin (A5-1), 70 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used instead of the raw materials used in Example 1. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were measured by the method described above.

[0363] The results are shown in Table 1. Additionally, antimicrobial persistence tests were conducted in water resistance category 0 and light resistance category 0 using the methods described above.

[0364] [Example 33]

[0365] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 25 parts by weight of ABS resin (A5-1), 75 parts by weight of magnesium oxide (B-2), and 0.6 parts by weight of unmodified polyolefin wax (C-1) were used to prepare samples for physical property testing in the same manner as in Example 1.

[0366] The results are shown in Table 1.

[0367] [Comparative Example 1]

[0368] As raw materials for the thermoplastic resin composition, instead of the raw materials used in Example 1, 68 parts by mass of propylene polymer (A2-2), 2.0 parts by mass of ethylene polymer (A1-3), 30 parts by mass of magnesium oxide (B-2), and 0.6 parts by mass of unmodified polyolefin wax (C-1) were used. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0369] The results are shown in Table 1. The composition obtained from Comparative Example 1 has poor thermal conductivity and therefore cannot transfer heat effectively, thus failing to achieve the high-end feel of ceramics.

[0370] [Comparative Example 2]

[0371] As raw materials for the thermoplastic resin composition, 23 parts by mass of propylene polymer (A2-2), 2.0 parts by mass of ethylene polymer (A1-3), 75 parts by mass of magnesium oxide (B-2), and 0.6 parts by mass of modified polyolefin wax were used instead of the raw materials used in Example 1. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the methods described above.

[0372] The results are shown in Table 1. The composition obtained from Comparative Example 2 showed a decrease in load flexural temperature and physical properties. This is believed to be because the modified polyolefin wax has a low acid value, resulting in weak hydrogen bonds with the metal oxide (hereinafter also referred to as filler), and uneven dispersion of the filler in the resin. On the other hand, it is believed that although the unmodified polyolefin wax (C) used in the examples has a weaker hydrogen bond with the filler due to its 0 acid value, its interaction with the small amount of resin acting as a binder is stronger, thus resulting in a composition with good load flexural temperature and physical properties.

[0373] [Comparative Example 3]

[0374] As raw materials for the thermoplastic resin composition, 23 parts by mass of propylene polymer (A2-2), 2.0 parts by mass of ethylene polymer (A1-3), and 75 parts by mass of magnesium oxide (B-2) were used instead of the raw materials used in Example 1. Otherwise, the same procedure as in Example 1 was followed to prepare samples for physical property testing, and the physical properties were determined by the method described above.

[0375] The results are shown in Table 1. The composition obtained from Comparative Example 3, due to the absence of unmodified polyolefin wax (C), was prone to filler agglomeration and uneven dispersion, making it difficult to manufacture, resulting in unevenness, poor compatibility, and poor resin flowability (MFR).

[0376] [Table 1-1]

[0377]

[0378] [Table 1-2]

[0379]

[0380] [Table 1-3]

[0381]

[0382] It should be noted that “※1” in Table 1 (Example 21) indicates that the thermoplastic resin composition is too fluid to be measured.

[0383] [Table 2]

[0384] Table 2

[0385]

[0386] [Table 3]

[0387] Table 3

[0388]

Claims

1. A thermoplastic resin composition comprising 10 to 40 parts by mass of a thermoplastic resin (A), 60 to 90 parts by mass of a metal oxide (B), and in the range of 0.1 to 20 parts by mass relative to 100 parts by mass of the total amount of (A) + (B) of an unmodified polyolefin-based wax (C), wherein, The total amount of (A) + (B) is set to 100 parts by mass, The metal oxide (B) contains magnesium oxide, The thermoplastic resin (A) is one or more selected from the group consisting of an ethylene-based polymer, a propylene-based polymer, a 1-butene-based polymer, a 4-methyl-1-pentene-based polymer, and an ABS-based resin.

2. The thermoplastic resin composition of claim 1, wherein, The average particle diameter of the metal oxide (B) is in the range of 0.1 to 110 μm.

3. The thermoplastic resin composition of claim 1, wherein, The thermal conductivity of the metal oxide (B) is in the range of 10 to 300 W / mK.

4. The thermoplastic resin composition of claim 1, wherein, The thermal conductivity of the thermoplastic resin composition is in the range of 0.5 to 5 W / mK.

5. The thermoplastic resin composition of claim 1, wherein, The specific gravity of the thermoplastic resin composition is in the range of 1.0 to 5.

0.

6. The thermoplastic resin composition as claimed in claim 1, comprising 10 to 30 parts by mass of the thermoplastic resin (A), and 70 to 90 parts by mass of the metal oxide (B), wherein, The total amount of (A) + (B) is set to 100 parts by mass.

7. The thermoplastic resin composition of claim 1, wherein, In an antibacterial test using Escherichia coli according to the membrane adhesion method described in JIS Z 2801:2012, the antibacterial activity value after 24 hours under the condition that no water resistance and light resistance pretreatment is performed is 2.0 or more.

8. The thermoplastic resin composition of claim 1, wherein, In an antibacterial test using Staphylococcus aureus according to the membrane adhesion method described in JIS Z 2801:2012, the antibacterial activity value after 24 hours under the condition that no water resistance and light resistance pretreatment is performed is 2.0 or more.

9. The thermoplastic resin composition of claim 1, wherein, In an antiviral test using Feline calicivirus according to ISO 21702:2019, the antiviral activity value is 2.0 or more.

10. The thermoplastic resin composition according to claim 1, which contains a fibrous filler (D) in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the total of the thermoplastic resin (A) and the metal oxide (B).

11. A molded body comprising the thermoplastic resin composition according to any one of claims 1 to 10.

12. A door handle, a spherical door pull, a handrail, or a switch comprising the thermoplastic resin composition according to any one of claims 1 to 10.

13. A housing comprising the thermoplastic resin composition according to any one of claims 1 to 10.

14. An accessory for clothing comprising the thermoplastic resin composition according to any one of claims 1 to 10.

15. A container comprising the thermoplastic resin composition according to any one of claims 1 to 10.

16. Stationery comprising the thermoplastic resin composition according to any one of claims 1 to 10.

17. Tableware or a wine ware comprising the thermoplastic resin composition according to any one of claims 1 to 10.

18. A mouse or a keyboard comprising the thermoplastic resin composition according to any one of claims 1 to 10.

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